Process for breaking petroleum emulsions



Patented Nov. 30, 1954 PROCESS FOR BREAKING PETROLEUM EMULSIONS NoDrawing. Application September 19, 1952, Serial No. 310,554

20 Claims. (Cl. 252-344) processes or procedures parbreaking orresolving and particularly petro- This invention relates to ticularlyadapted for preventing, emulsions of the water-in-oil type,

leum emulsions.

The present invention is a continuation-in-part of my co-pendingapplications, Serial Nos. 288,745, filed May 19, 1952, 296,086, filedJune 27, 1952, and 301,806, filed July 30, 1952.

My invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type, that are commonly referredto as cut oil, emulsified oil, roily oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

The demulsifying agents employed in the present demulsifying process arethe products obtained by the process of first condensing (a) Anoxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin of thetype described hereinafter in Part 1.

(b) A basic hydroxylated polyamine having at least one secondary aminogroup and having not over 32 carbon atoms in any radical attached to anyamino nitrogen atom, and with the further proviso that the polyamine befree from any primary amino radical, any substituted imidazolineradical, and any substituted tetrahydropyrimidine radical; and

(c) Formaldehyde;

said condensation reaction being conducted at a temperature sufficientlyhigh to eliminate water and below the pyrolytic point of the reactantsand resultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heatstable andoxyalkylation-susceptible. The condensation reaction is followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide to form the present demulsifying agents.

In many instances and for various purposes, particularly for theresolution of petroleum emulsions of the water-in-oil type, one maycombine a comparatively large proportion of the alkylene oxide,particularly propylene oxide or a combination of propylene oxide andethylene oxide, with a comparatively small proportion of the resincondensate. In some instances the ratio by weight has been as high as50-to-1, i. e., the ultimate product of reaction containingapproximately 2% of resin condensate and approximately 98% of alkyleneoxide.

This invention in a more limited aspect as far as the reactants areconcerned which are subjected to oxyalkylation are certainamine-modified thermoplastic phenol-aldehyde resins. Such amine-modifiedresins are described in the aforementioned co-pending applications andmuch that is said herein is identical with the text of saidaforementioned co-pending applications; however, some detail is omittedsince the art is aware of these resins through my mentioned copendingapplications, e. g., S. N. 296,086. For purpose of simplicity theinvention, purely from a standpoint of the resin condensate involved,may be exemplified by an idealized formula R R n rt in which Rrepresents an aliphatic hydrocarbon substituent generally having fourand not over 18 carbon atoms but most preferably not over 14 carbonatoms, and n generally is a small whole number varying from 1 to 4. Inthe resin structure it is shown as being derived from formaldehydealthough obviously other aldehydes are equally satisfactory. The amineresidue in the above structure is derived from a hydroxylated basicpolyamine and usually a strongly basic polyamine having at least onesecondary amino radical and free from any primary amino radical, anysubstituted imidazoline radical and any substituted tetrahydropyrimidineradical, and may be indicated thus represents any appropriatehydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical,etc., with the proviso that at least one occurrence of R contains anamino radical which is not part of a primary amino radical or part of asubstituted imidazoline radical or part of a substitutedtetrahydropyrimidine radical, and with the further proviso that there bepresent at least one hydroxylated hydrocarbon radical such as a hydroxylalkyl radical, a hydroxy alicyclic radical, a hydroxy alkylaryl radical,etc. Such hydroxylated radical need not be limited to a single hydroxylgroup as in the case of an alkanol radical but may include 2 or morehydroxyl groups, such as a glycerol derivative 01', in essence, adihydroxy propyl group.

Actually, what has been depicted in the formula above is only anover-simplified exemplification of that part of the polyamine which hasthe reactive secondary amino group. Actually, a more completeillustration is obtained by reference to oxyalkylated derivativesobtained by the oxyethylation or oxypropylation, for example, ofsubstituted polyalkylene amines of the following structure:

in which R in which R has its prior significance, R" represents ahydrogen atom or radical R, D is a hydrogen atom or an alkyl group, nrepresents the numerals l to 10, and x represents a small whole numbervarying from 1 to 7 but generally from 1 to 3, with the proviso that theother previously stated requirements are met. See U. S. Patent No.2,250,176 dated July 22, 1941, to Blair. Reaction with an alkyleneoxide, such as ethylene oxide or propylene oxide must of course be surethat the derivative so obtained still has at least one secondary aminohydrogen group, all of which will be illustrated by numerous examplessubsequently.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Brittonet al., which describes alkylene diamines and polymethylene diamineshaving the formula where R represents an alkyl, alkenyl, cycloalkyl, oraralkyl radical and n represents a comparatively small integer such as lto 8. Such compound as the one just described can be reacted with asingle mole of ethylene oxide or propylene oxide or glycide to give asuitable reactant.

A further limitation in light of the required basicity is that thesecondary amino radical shall not be directly joined to an aryl radicalor acyl radical or some other negative radical. Needless to say, whathas been stated above in regard to the groups attached to nitrogen isnot intended to exclude an oxygen-interrupted carbon atom linkage or aring linkage as in the instance of compounds obtained by converting anN-aminoalkylmorpholine of the formula where n is a whole number from 2to 12 inclusive, and the nitrogen atoms are separated by at least twocarbon atoms, into a secondary amine by means of an alkylene oxide, suchas ethylene oxide, propylene oxide, or glycide, so as to yield acompound such as The introduction of two such hydroxylated polyamineradicals into a comparatively small resin molecule, for instance, onehaving 3 to 6 phenolic nuclei as specified, alters the product in anumber of ways. In the first place, a basic nitrogen atom, of course,adds a hydrophile effect; in the second place, depending on the size ofthe radical R, there may be a counter-balancing hydrophobe effect or onein which the hydrophobe effect more than counterbalances the hydrophileeffect of the nitrogen atom. Finally, in such cases where R contains oneor more oxygen atoms, another effect is introduced, particularly anotherhydrophile effect. In the present procedure the polyamine reactantinvariably has at least one hydroxyl group and also may have areoccurring ether linkage, all of which in turn affects the hydrophileproperties.

I am not aware that it has been previously suggested to modify byoxyalkylation the resin condensates of the kind described and in mycopending application S. N. 296,086. The condensation product obtainedaccording to the present invention is heat stable and, in fact, one ofits outstanding qualities is that it can be subjected to oxyalkylation,particularly oxyethylation or oxypropylation, under conventionalconditions, i. e., presence an alkaline catalyst, for example, but inany event at a temperature above 100 C. without becoming an insolublemass.

Any reference, as in the hereto appended claims, to

the procedure employed in the process is not intended to limit themethod or order in which the reactants are added, commingled or reacted.The procedure has been referred to as a condensation process for obviousreasons. As pointed out elsewhere it is my preference to dissolve theresin in a suitable solvent, add the amine, and then add theformaldehyde as a 37% solution. However, all three reactants can beadded in any order. I am inclined to believe that in the presence of abasic catalyst, such as the amine employed, that the formaldehydeproduces methylol groups attached to the phenolic nuclei which, in turn,react with the amine. It would be immaterial, of course, if the.formaldehyde reacted with the amine so as to introduce a methylol groupattached to nitrogen which, in turn, would react with the resinmolecule. Also, it would be immaterial if both types of compounds wereformed which reacted with each other with the evolution of a mole offormaldehyde available for further reaction. Furthermore, a reactioncould take place in which three different molecules are simultaneouslyinvolved although, for theoretical reasons, that is less likely. What issaid herein in this respect is simply by way of explanation to avoid anylimitation in regard to the appended claims.

Actually, what has been said previously is not as complete an idealizedpresentation as is desirable due to another factor involved. The factoris this. Since the polyamine is hydroxylated and although it may have atertiary amine group which is not susceptible to oxyalkylation, it mayhave more than one secondary group and thus the amine residue per se iscertain to have at least one hydroxyl group and perhaps more than oneand may have a labile hydrogen atom attached to nitrogen. Actually, itis diificult. to statev in general terms what the susceptibility of asecondary nitrogen group is under the conditions described for reasonswhich are obscure. Briefly stated, oxyalkylation seems to proceedreadily at terminal secondary amino groups but less readily andsometimes hardly at all whenthe same group appears in the center of alarge molecule. In the instant situation there are phenolic hydroxylgroups available which are readily susceptible to oxyalkylation and alsohydroxyl groups in the amino radical. If one assumes for the moment thatthe hydroxylated amine radical contains at least one or possibly twohydroxyls and if one ignores the oxyalkylation susceptibility of anysecondary amino groups present, then the condensate can be depicted moresatisfactorily in the following manner by first referring to the resincondensate and then to the oxyalkylated derivative:

in which for simplicity the formula just shown previously has beenlimited to the specific instance where there is one oxyalkylationsusceptible hydroxyl radical as part of the polyamine residue.

In the above formula R"O is the radical of an alkylene oxide such as theethoxy, propoxy or similar radicals derived from ethylene oxide,propylene oxide, glycide or the like, andn is a number varying from 1 to60, with the proviso that one need not oxyalkylate all the availablephenolic hydroxyl radicals or all the available amino hydrogen atoms tothe extent they are present. In other words, one need convert only twolabile hydrogen radicals per condensate. It is immaterial whether thelabile hydrogen atoms be attached to oxygen or nitrogen.

As far as the use of the herein described ultimate products goes forpurpose of resolution of petroleum emulsions of the water-in-oil type, Iparticularly prefer to use those which as such merely as a result ofoxyalkylation alone, or in the form of the free base or hydrate, i. e.,combination with water or particularly in the form of a low molalorganic acid such as the acetate or hydroxy acetate, have suflicientlyhydrophile character to at least meet the test set forth in U. S. PatentNo. 2,499,368, dated March 7, 1950, to De Groote et al. In someinstances oxyalkylation is the controlling factor rather than the basicnitrogen atoms present regardless of their structure or combination. Insaid patent such test for emulsification using a water-insoluble solventgenerally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated condensation productsas such or in the form of the free base or in the form of the acetate,may not necessaril be xylene-soluble although they are in many instancesIf such compounds are not xylene-soluble the obvious chemical equivalentor equivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases on vigorous shaking andsurface activity makes its presence manifest. It is understood thereference in the hereto appended claims as to the use of xylene in theemulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368, dated March 7, 1950,to De Groote and Keiser. In said immediately aforementioned patent thefollowing test appears:

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with 1-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysuflicient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-inwater type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,

particularly in the lowest stage of oxyalkylation, one may obtain awater-in-xylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and further dilution with water. If in doubt as tothis property, comparison with a resin obtained from para-tertiarybutylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde)using an acid catalyst and then followed by oxyalkylation using 2 molesof ethylene oxide for each phenolic hydroxyl, is helpful. Such resinprior to oxyalkylation has a molecular weight indicating about 4 /2units per resin molecule. Such resin, when diluted with an equal weightof xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposeof this test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With border-line cases, i. e., thosewhich show only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is 6 capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebutylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or an equivalent water-insoluble solvent may maskthe point at which a solventfree product on mere dilution in a test tubeexhibits self-emulsification. For this reason, if it is desirable todetermine the approximate point where self-emulsification begins, thenit is better to eliminate the xylene or equivalent from a small portionof the reaction mixture and test such portion. In some cases, suchxylene-free resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientselfemulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added waterinsoluble solvent and minor proportionsof common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely producesan emulsion.

Having described the invention briefly and not necessarily in its mostcomplete aspect, the text immediately following will be a more completedescription with specific reference to reagents and the method ofmanufacture.

For convenience the subsequent text will be divided into five parts:

Part 1 is concerned with the general structure of the amine-modifiedresin condensates and also the resin itself, which is used as a rawmaterial;

Part 2 is concerned with appropriate basic hydroxylated polyarnineswhich may be employed in the preparation of the herein describedamine-modified resins or condensates;

Part 3 is concerned with the condensation reactions involving the resin,the amine, and formaldehyde to produce the specific products orcompounds;

Part 4 is concerned with the oxyalkylation of the products described inPart 3, preceding; and

Part 5 is concerned with the use of the oxyalkylated amine-modifiedresins obtained as described in Part 4, preceding, for use in theresolution of emulsions of the water-in-oil type.

In the subsequent text, Parts 1, 2 and 3 appear in substantially thesame form as in the text of the aforementioned co-pending applications,Serial Nos. 288,745, filed May 19, 1952, 296,086, filed June 27, 1952,and 301,806, filed July 30, 1952. Furthermore, Part 4 is essentially thesame as Part 4 in the last aforementioned co-pending application, i. e.,Serial No. 301,806, filed July 30, 1952.

PART 1 It is well known that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form by theformula H OH H1 OH R R n R In the above formula n represents a smallwhole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or12 units, particularly when the resin is subjected to heating under avacuum as described in the literature. A limited sub-genus is in theinstance of low molecular weight polymers where the total number ofphenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; Rrepresents an aliphatic hydrocarbon substituent, generally an alkylradical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl,decyl or dodecyl radical. Where the divalent bridge radical is shown asbeing derived from formaldehyde it may, of course, be derived from anyother reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance para-phenylphenol, one may obtain a resin which is not solublein a nonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol, dioxane, ordiethylglycol diethylether. Sometimes a mixture of the two solvents(oxygenated and nonoxygenated) will serve. See Example 9a of U. S.Patent No. 2,499,365, dated March 7, 1959, to De Groote and Keiser.

The resin herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexylene or benzene-soluble as described in aforementioned U. S. PatentNo. 2,499,365, or in U. S. Patent No. 2,499,368. dated March 7, 1950, toDe Groote and Keiser. In said patent there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resinshaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule. The phenol aldehyde resinsare difunctional only in regard to methylol-forming reactivity, and theresins are derived by reaction between a difunctional monohydric phenoland an aldehyde having not over 8 carbon atoms and reactive toward thephenol. Also, the resins are formed in the substantial absence oftrifunctional phenols. The phenol constituent of the resins is of theformula in which R is an aliphatic hydrocarbon radical having at least 4carbon atoms and not more than 24 carbon atoms and substituted in the2,4,6 position.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic hydroxylated polyamine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thus:

R R n R The basic polyamine may be designated thus:

R! HN subject to what has been said previously as to the presence of atleast one amine radical in at least one occurrence of R with theproviso, as previously stated, that the amine radical be other than aprimary amine radical, a substituted imidazoline radical or asubstituted tetrahydropyrimidine radical, with the proviso that theremust be present at least one hydroxyl radical as part of at least one ofthe occurrence of R. However, if one attempts to incorporate into theformula a structure such as an oxyethylated or oxypropylated derivativeof a substituted polyalkyleneamine of the following type:

R R N-CnH2n-(CnH2nN-D)ZN\ 8 in which the various characters have thesame significance as 1n initial presentation of this formula, then onebecomes involved in added difficulties in presenting an overall picture.Thus, for sake of simplicity, the hydroxylated polyamine will bedepicted as RI HN subject to the limitation and explanation previouslynoted.

In conducting reactions of this kind one does not necessarily obtain ahundred per cent yield for obvious reasons. Certain side reactions maytake place. For instance, 2 moles of amine may combine with one mole ofthe aldehyde, or only one mole of the amine may combine with the resinmolecule, or even to a very slight extent, if at all, 2 resin units maycombine without any amine in thelreaction product, as indicated in thefollowing formu as:

R R nR R R R n R As has been pointed out previously, as far as the resinunit goes one can use a mole of aldehyde other than formaldehyde, suchas acetaldehyde, propionaldehyde or in which R is the divalent radicalobtained from the particular aldehyde employed to form the resin. Forreasons which are obvious the condensation product obtained appears tobe described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although I have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few 10ths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trimer and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

TABLE I osiw o R tlon of R gg l n resin R molecule 3. 5 992. 5 3. 5 882.5 3. 5 882. 5 3. 5 1, 025. 5 Tertiary amyl 3. 5 959.5 Mixed secondaryand 3. 5 805. 5

tertiary amyl.

7a.-.. Propyl 3. 5 805. 5 8a Tertiary hexyl 3. 5 1, 036. 5 9a ctyl 3. 51,190. 5 la Nony1 3. 1, 267. 5 11a... Decyl..- 3. 5 1, 344. 5 12aDodecyl 3. 5 1, 498. 5 13a... Tertiary butyl 3. 5 945. 5 14a..- Tertiaryamyl 3. 5 1, 022. 5 15a on 3.5 1, 330. 5 16a... Tertiary butyL 3. 5 1,071. 5 17a Tertiary amyl. 3. 5 1, 148. 5 18a on 3. 5 1, 456.5 19a...Tertiary butyl d 3. 5 1,008. 5 20a Tertiary amyl do 3. 5 1, 085. 5 2laNonyl 3. 5 1, 393. 5 22a... Tertiary butyl- 4. 2 996. 6 23a TertiaryamyL. 4. 2 1, 083. 4 4. 2 1, 430. 6 4. 8 1, 094. 4 4. s 1, 189. 6 4. 81, 570. 4

PART 2 As has been pointed out, the amine herein employed as a reactantis a hydroxylated basic polyamine and preferably a strongly basicpolyamine having at least one secondary amino radical, free from primaryamino groups, free from substituted imidazoline groups, and free fromsubstituted tetrahydropyrimidine groups, in which the hydrocarbonradicals present, whether monovalent or divalent are alkyl, alicyclic,arylalkyl, or heterocyclic in character, subject of course to theinclusion of a hydroxyl group attached to a carbon atom which in turn ispart of a ,monovalent or divalent radical.

Previous reference has been made to a number of polyamines which aresatisfactory for use as reactants in the instant condensation procedure.They can be obtained by hydroxyalkylation of low cost polyamines. Thecheapest amines available are polyethylene amines and polypropyleneamines. In the case of the polyethylene amines there may be as 5, 6 or 7nitrogen atoms. Such amines are susceptible to terminal alkylation orthe equivalent, i. e., reactions which convert the terminal primaryamino group or groups into a secondary or tertiary amine radical. In thecase of polyamines having at least 3 nitrogen atoms or more, bothterminal groups could be converted into tertiary groups, or one terminalgroup could be converted into a tertiary group and the other into asecondary amine group. In the same way, the polyaminescan be subjectedto hydroxyalkylation by reaction with ethylene oxide, propylene oxide,glycide, etc. In some instances, depending on the structure, both typesof reaction may be employed, i. e., one type to introduce a hydroxylethyl group, for example, and another type to introduce a methyl orethyl radical.

By way of example the following formulas are included. It will be notedthey include such polyamines which, instead of being obtained fromethylene dichloride, propylene dichloride, or the like, are obtainedfrom dichloroethyl ethers in which the divalent radical has a carbonatom chain interrupted by an oxygen atom:

HOC2H4 OZHIOH HOCzH4 H NpropyleneNpropyleneN Another procedure forproducing suitable polyamines is a reaction involving first an alkyleneimine, such as ethylene imine or propylene imine, followed by analkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involvinga secondary alkyl amine, or a secondary aralkyl amine, or a secondaryalicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine,or mixed amines with an imine so as to introduce a primary amino groupwhich can be reacted with an alkylene oxide followed by reaction with animine and then the use of an alkylene oxide again. Similarly, one canstart with a primary amine and introduce two moles of an alkylene oxideso as to have a compound comparable to ethyl diethanolamine and reactwith two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., asuitable secondary monoamine plus an alkylene imine plus an alkyleneoxide, or a suitable monoamine plus an alkylene oxide plus an alkyleneimine and plus the second introduction of an alkylene oxide, can beapplied to a variety of primary amines. In the case of primary aminesone can either employ two moles of an alkylene oxide so as to convertboth amino hydrogen atoms into an alkanol group, or the equivalent; orelse the primary amine can be converted into a secondary amine by thealkylation reaction. In any event, one can obtain a series of primaryamines and corresponding secondary amines which are characterized by thefact that such amines include groups having repetitious ether linkagesand thus introduce a definite hydrophile efiect by virtue of the etherlinkage. Suitable polyether amines susceptible to conversion in themanner described include those of the formula HO CzHt in which x is asmall whole number having a value of 1 or more, and may be as much as 10or 12; n is an integer having a value of 2 to 4, inclusive; m representsthe numeral 1 to 2; and m represents a number 0 to 1, with the provisothat the sum of m plus m equals 2; and R has its prior significance,particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature andparticularly in two United States patents, to wit, U. S. Nos. 2,325,514,dated July 27, 1943, to Hester, and 2,355,337 dated August 8, 1944, toSpence. The latter patent describes typical haloalkyl ethers such asSuch haloalkyl ethers can react with ammonia, or with a primary aminesuch as methylamine, ethylamine, cyclohexylamine, etc., to produce asecondary amine of the kind above described, in which one of the groupsattached to nitrogen is typified by R. Such haloalkyl ethers also can bereacted with ammonia to give secondary amines as described in the firstof two patents mentioned immediately preceding. Monoamines so obtainedand suitable for conversion into appropriate polyamines are exemplifiedby CHsOCHzCHzCHzCHzCHzCHz) 2NH.

Other similar secondary monoamines equally suitable for such conversionreactions in order to yield appropriate secondary amines, are those ofthe composition as described in U. S. Patent No. 2,375,659, dated May 8,1945, to Jones et al. In the above formula R may be methyl, ethyl,propyl, amyl, octy etc.

Other suitable secondary amines which can be converted into appropriatepolyamines can be obtained from products which are sold in the openmarket, such as may be obtained by alkylation of cyclohexylmethylamineor the alkylation of similar primary amines, or for that matter, aminesof the kind described in U. S. Patent No. 2,482,546, dated September 20,1949, to Kaszuba, provided there is no negative group or halogenattached to the phenolic nucleus. Examples include the following: betaphenoxyethylamine, gamma phenoxypropylamine,beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines arethe kind described in British Patent No. 45 6,5 17, and may beillustrated by In light of the various examples of polyamines which havebeen used for illustration it may be well to refer again to the factthat previously the amine was shown as R! with the statement that suchpresentation is an over-simplification. rence of R must include asecondary amino radical of the kind specified. Actually, if thepolyamine radical contains two or more secondary amino groups the aminemay be reactive at two different positions and thus the same amine mayyield compounds in which R and R are dissimilar. This is illustrated byreference to two prior examples:

CZHLOH CH3 CH3 In the first of the two above formulas if the reactioninvolves a terminal amino hydrogen obviously the radicals attached tothe nitrogen atom, which in turn combines with the methylene bridge,would be different than if the reaction took place at the intermediatesecondary amino radical as differentiated from the terminal group.Again, referring to the second formula above, although a terminal aminoradical is not involved it is obvious again that one could obtain twodifferent structures for the radicals attached to the nitrogen atomunited to the methylene bridge, depending on whether the reaction tookplace at either one of the two outer secondary amino groups, or at thecentral secondary amino group. If there are two points of reactivitytowards formaldehyde as illustrated by the above examples it is obviousthat one might get a mixture in which in part the reaction took place atone point and in part at another point. Indeed, there are well knownsuitable polyamine reactions where a large variety of compounds might beob- It was pointed out that at least one occur- 4 tained due to suchmultiplicity of reactive radicals. can be illustrated by the followingformula:

Certain hydroxylated polyamines which may be employed and whichillustrate the appropriate type of reactant used for the instantcondensation reaction may be illustrated by the following additionalexamples:

This

Over and above the specific examples which have appeared previously,attention is directed to the fact that a number of suitable amines areincluded in subsequent completely neutralized at the end of thereaction. The molecular weight of the resin was 882.5. This correspondedto an average of about 3%. phenolic nuclei, as

Table II. the value for n which excludes the two external nuclei, PART 3i. 3,4 the 1resin largely a mixturelhaving 3 nuclei The productsobtained by the herein described procan Due 61 eec u mg t two eXt-emanuclel or 5 and esses represent cogeneric mixtures which are the resultE ???i g i ggg e fi g so obtamed a neutral state of a condensatlonreaction or reactions. Since the resin 882 grams of the resin identifiedas 2a preceding, molecule cannot be defined satisfactorily by formula,were powdered and mixed with a eonsiderabl lesser although it may be soillustrated in an idealized simplifiweight of Xylene to wit 500 gramsThe mixtgre was canon It Is l l to actually qepict the final Productrefluxed until solution was complete. It was then adggetltlge cogenericmixture except in terms of the process jlsted to e g zg g 31 5801301" ge296 grams o symmetrica 1 y roxye y et y ene iamine were Prevlousreference has e made to the f that the added. The mixture was stirredvigorously and formal- Proeedure employed 1s Comparable m general dehydeadded slowly. In this particular instance the f n that whleh correspondsto Somewhat 5 formaldehyde used was a 30% solution and the amountrlvatiyes made either from phenols as differentiated from employed was200 grams It was added in a little over a resm P 111 the manufacture aphenol'amlne'alde' 3 hours. The mixture was stirred vigorously and kepty T6513} else from a PaT t1c111aT1Y Selected Tesln within a temperaturerange of 33 to 48 C. for about 'f an amlne and formaldehyde lnfhe mannerdescribed 17 hours. At the end of this time it was refluxed using 1113111501} 2,03 L557 orfief to Obtam a a phase-separating trap and a smallamount of aqueous heat-reactive resin. Since the condensation productsobdistillate Withdrawn f time to time The presence tained are notheat-convertible and since manufacture is f f ld h d was noted Anyunreacted f 1d not restrlcted to aosmgle phase y and smce hyde seemed todisappear within about 3 hours or P p t0 150 0r thefeabollts y be p qy ithereabouts. As soon as the odor of formaldehyde was 15 that thePf9cedure Pecomes comearatlvely no longer particularly noticeable ordetectible the phasep T1118 Procedure 18 noted In y copendmg PPseparating trap was set so as to eliminate part of the cation N.296,036, and further descflptlon 0f ceftaln xylene was removed until thetemperature reached apdew-11S 1S unnecessary proximately 150 C. orperhaps a little higher. The Needless 9 y as r as the r p f reactants greaction mass was kept at this temperature for a little I havelnvarlably p y appfoXlmatelY 0116 111016 of over 4 hours and thereaction stopped. During this the resin based on the molecular weight ofthe resin moletime any additional water, which was probably water cule,2 1110165 of the seconflafy p ly min and 2 11 1 f of reaction which hadformed, was eliminated by means formaldehyde. In some instances I haveadded a trace of the trap. The residual xylene was permitted to stay ofcaustic as an added catalyst but have found no parin the cogenericmixture. A small amount of the ticular advantage in this. In other casesI have used sample was heated on a water bath to remove the excess aslight excess of formaldehyde and, again, have not xylene. The residualmaterial was dark red in color found any particular advantage in this.In other cases, and had the consistency of a sticky fluid or tackyresin. I have used a slight excess of amine and, again, have not Theoverall time for reaction was somewhat under 30 found any particularadvantage in so doing. Whenever hours. In other examples it varied from24 to more feasible I have checked the completeness of reaction in than36 hours. The time can be reduced by cutting the the usual ways,including the amount of water of reaclow temperature period toapproximately 3 to 6 hours. tion, molecular weight, and particularly insome instances Note that in Table II following there are a large numhavechecked whether or not the end-product showed surher of added examplesillustrating the same procedure. face-activity, particularly in a diluteacetic acid solution. In each case the initial mixture was stirred andheld at a The nitrogen content after removal of unreacted polyfairly lowtemperature (30 to 40 C.) for a period amine, if any is present, isanother index. of several hours. Then refluxing was employed until Inlight of what has been said prevviously, little more the odor offormaldehyde disappeared. After the odor need be said as to the actualprocedure employed for of formaldehyde disappeared the phase-separatingtrap the preparation of the herein described condensation was employedto separate out all the water, both the products. The following examplewill serve by way of solution and condensation. After all the water hadbeen illustration: separated enough xylene was taken out to have thefinal Exam 12 1b product reflux for several hours somewhere in the rangep of 145 to 150 C., or thereabouts. Usually the mixture Thephenol-aldehyde resin is the one that has been identified previously asExample 2a. It was obtained from a partertiary butyl phenol andformaldehyde. The resin was prepared using an acid catalyst which wasyielded a clear solution by the time the bulk of the water, or all ofthe water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24examples in Table II.

TABLE II Strength of Max. dis- Ex. Resm Amt, Amme used and Solvent usedReaction 383051011 No. used grs. amount gfgz g ggg g and amt. temp., C.tlrne (hrs) e b 882 Amine A, 296 g 30%, 200 g..." Xylene, 500 gr...21-24 24 150 480 Amine A, 148 g 37%, 81 g Xylene, 480 g. 20-23 27 156633 0 do Xylene, 610 22-27 25 142 441 Amine B, 176 g Xylene, 300 g 20-2528 145 480 do 7%, g Xylene, 425 g 23-27 34 150 633 .do 30%, g Xylene,500 g 25-27 30 152 882 Amine O, 324 g... 37%, 162 g. Xylene, 625 g.23-26 38 141 480 Amine O, 162 g 7 Xylene, 315 g 20-21 25 143 d Xylene,535 g.... 23-24 25 Xylene, 425 15.... 22-25 25 148 Xylene, 450 g 20-2125 158 Xylene, 525 g 21-25 28 152 Xylene, 400 g 22-24 26 143 do 25-27 36144 Xylene, 500 g 26-27 34 141 Xylene, 400 g 21-23 25 153 do 20-22 28 doXylene, 500 g 23-25 27 155 409 Amine G 172 Xylene, 400 g. 20-21 34 150542 do Xylene, 450 g 20-24 36 152 547 Amine H, 221 g Xylene, 500 g 20-2230 148 441 do Xylene, 400 g 20-28 24 143 595 Amine I, 172 g .do..Xylene, 450 g 20-22 32 151 391 Amine I, 86 g 30%, 50 g Xylene, 300 g20-26 36 147 HO CHzCHzNHCH HOCHzCHzNH-CHz Amine H CHsNHCHz CHaNHCHz-CCHzOH C HaNH C H2 Amine I PART 4 In preparing oxyalkylated derivativesof products of the kind which appear as examples in Part 3, I have foundit particularly advantageous to use laboratory equipment which permitscontinuous oxypropylation and oxyethylation. More specific referencewill be made to treatment with glycide subsequently in the text. Theoxyethylation step is, of course, the same as the oxypropylation stepinsofar that two low boiling liquids are handled in each instance. Whatimmediately follows refers to oxyethylation and it is understood thatoxypropylation can be handled conveniently in exactly the same manner.

The oxyethylation procedure employed in the preparation of derivativesof the preceding intermediates has been uniformly the same, particularlyin light of the fact that a continuous operating procedure was employed.In this particular procedure the autoclave was a conventional jacketedautoclave, made of stainless steel and having a capacity ofapproximately 25 gallons, and a working pressure of 300 pounds gaugepressure. The autoclave was equipped with the conventional devices andopenings, such as the variable speed stirrer operating at speeds from 50R. P. M. to 500 R. P. M., thermometer well and thermocouple for recordercontroller; emptying outlet, pressure gauge, manual and rupture discvent lines; charge hole for initial reactants; at least one connectionfor conducting the incoming alkylene oxide, such as ethylene oxide, tothe bottom of the autoclave; along with suitable devices for bothcooling and heating the autoclave through the jacket. Also, I prefercoils in addition thereto, with the coils so arranged that they aresuitable for heating with steam or cooling with water, and the jacketfurther equipped with electrical heating devices, such as are employedfor hot oil or Dowtherm systems. Dowtherm, more specifically Dowtherm A,is a colorless non-corrosive liquid consisting of an eutectic mixture ofdiphenyl and diphenyl oxide. Such autoclaves are, of course, in essence,small scale replicas of the usual conventional autoclave used incommercial oxyalkylatin'g procedure.

Continuous operation, or substantially continuous operation, is achievedby the use of a separate container to hold the alkylene oxide beingemployed, particularly ethylene oxide. The container consistsessentially of a laboratory bomb having a capacity of about 10 to 15gallons or somewhat in excess thereof. This bomb was equipped, also,with an inlet for charging, and an outlet tube going to the bottom ofthe container so as to permit discharging of alkylene oxide in theliquid phase to the autoclave. Other conventional equipment consists, ofcourse, of the rupture disc, pressure gauge, sight feed glass,thermometer, connection for nitrogen for pressuring bomb, etc. The bombwas placed on a scale during use and the connections between the bomband the autoclave were flexible stainless hose or tubing so thatcontinuous weighings could be made without breaking or making anyconnections. This also applied to the nitrogen line, which was used topressure the bomb reservoir. To the extent that it was required, anyother usual conventional procedure or addition which provided greatersafety was used, of course, such as safety glass, protective screens,etc.

With this particular arrangement practically all oxyethylations becameuniform in that the reaction temperature could be held within a fewdegrees of any selected point in this particular range. In the earlystages where the concentration of catalyst is high the temperature wasgenerally set for around C. or thereabouts. Subsequently the temperaturemay be somewhat higher for instance, C. to C. Under other conditions,definitely higher temperatures may be employed, for instance 170 C. to175 C. It will be noted by examination of subsequent examples that thistemperature range was satisfactory. In any case, where the reaction goesmore slowly a higher temperature may be used, for instance, 140 C. toC., and if need be C. to C. Incidentally, oxypropylation takes placemore slowly than oxyethylation as a rule and for this reason I have useda temperature of approximately 135 C. to 140 C., as being particularlydesirable for initial oxypropylation, and have stayed within the rangeof 130 C. to 135 C. almost invariably during oxypropylation. The lesserreactivity of propylene oxide compared with ethylene oxide can be ofisetby use of more catalyst, more vigorous agitation and perhaps a longertime period. The ethylene oxide was forced in by means of nitrogenpressure as rapidly as it was absorbed as indicated by the pressuregauge on the autoclave. In case the reaction slowed up the temperaturewas raised so as to speed up the reaction somewhat by use of extremeheat. If need be, cooling water was employed to control the temperature.

As previously pointed out in the case of oxypropylation asdifferentiated from oxyethylation, there was a tendency for the reactionto slow up as the temperature dropped much below the selected point ofreaction, for instance, 135 C. In this instance, the technique employedwas the same as before, that is, either cooling water was cut down orsteam was employed, or the addition of propylene oxide speeded up, orelectric heat used in addition to the steam in order that the reactionproceeded at, or near, the selected temperatures to be maintained.

Inversely, if the reaction proceeded too fast regardless of theparticular alkylene oxide, the amount of reactant being added, such asethylene oxide, was cut down or electrical heat was cut off, or steamwas reduced, or if need be, cooling water was run through both thejacket and the cooling coil. All these operations, of course, aredepending on the required number of conventional gauges, check valves,etc., and the entire equipment, as has been pointed out, is conventionaland, as far as I am aware can be furnished by at least two firms whospecialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: (a) If prepared from glycerol monochlorohydrin, this productshould be comparatively pure; (b) the glycide itself should be as pureas possible as the effect of impurities is difiicult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptly as introduced, i. e., that no excess ofglycide is allowed to accumulate; (d) all necessary precautions shouldbe taken that glycide cannot polymerize per se; (e) due to the highboiling point of glycide one can readily employ a typical separatableglass resin pot as described in U. S. Patent No. 2,499,370, dated March7, 1950, and offered for sale by numerous laboratory supply houses. Ifsuch arrangement is used to prepare laboratory scale duplications, thencare should be taken that the heating mantle can be removed rapidly soas to allow for cooling; or better still, through an added opening atthe top, the glass resin pot or comparable vessel should be equippedwith a stainless steel cooling coil so that the pot can be cooled morerapidly than mere removal of mantle. If a stainless steel coil isintroduced it means that conventional stirrer of the paddle type ischanged into the centrifugal type which causes the fluids or reactantsto mix due to swirling action in the center of the pot.. Still better,is the use of a laboratory autoclave of the kind previously described inthis part of the text, but in any event, when the initial amount ofglycide is added to a suitable reactant, such as the herein describedamine-modified phenol-aldehyde resin, the speed of reaction should becontrolled by the usual factors, such as (a) the addition of glycide;(b) the elimination of external heat and use of cooling coil so there isno undue rise in temperature. All the foregoing is merely conventionalbut is included due to the hazard in handling glycide.

Although ethylene oxide and propylene oxide may represent less of ahazard than glycide, yet these reactants should be handled with extremecare. One suitable procedure involves the use of propylene oxide orbutylene oxide as a solvent as well as a reactant in the earlier stagesalong with ethylene oxide, for instance, by dissolving the appropriateresin condensate in propylene oxide even though oxyalkylation is takingplace to a greater or lesser degree. After a solution has been ob tainedwhich represents the selected resin condensate dissolved in propyleneoxide or butylene oxide, or a mixture which includes the oxyalkylatedproduct, ethylene oxide is added to react with the liquid mass untilhydrophile properties are obtained, if not previously present to thedesired degree. Indeed hydrophile character can be reduced or balancedby use of some other oxides such as propylene oxide or butylene oxide.Since ethylene oxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide which can be eliminated by volatilization or distillationin any suitable manner. See article entitled Ethylene oxide hazards andmethods of handling, Industrial and Engineering Chemistry, volume 42,No. 6, June 1950, pp. 1251-1258. Other procedures can be employed as,for example, that described in U. S. Patent No. 2,586,767, datedFebruary 19, 1952, to Wilson.

Example The oxyalkylation-susceptible compound employed is the onepreviously described and designated as Example lb. Condensate 1b was inturn obtained from symmetrical di(hydroxyethyl)ethylene diamine,previously described for convenience as Amine A, and the resinpreviously identified as Example 2a. Reference to Table I shows thatthis particular resin is obtained from paratertia'rybutylphenol andformaldehyde. 12.02 pounds of this resin condensate were dissolved in 5pounds of solvent (xylene) along with one pound of finely powderedcaustic soda as a catalyst. Adjustment was made in the autoclave tooperate at a temperature of approximately 130 C. to 135 C., and at apressure of about to pounds. In some subsequent examples pressures up to35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide inapproximately 1% hours, and then continue stirring for 15 minuteslonger. The reaction went readily and, as a matter of fact, the oxidewas taken up almost immediately. Indeed the reaction was complete inless than an hour. The speed of reaction, particularly at the lowpressure, undoubtedly was due in a large measure to excellent agitationand also to the comparatively high concentration of catalyst. The amountof ethylene oxide introduced was equal in weight to the initialcondensation product, to wit, 12.02 pounds. This represented a molalratio of 27.3 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was2404. A comparatively small sample, less than 50 grams, was withdrawnmerely for examination as far as solubility or emulsifying power wasconcerned and also for the purpose of making some tests on various oilfield emulsions. The amount withdrawn was so small that no cognizance ofthis fact is included in the data, or subsequent data, or in the datapresented in tabular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerablecomparable oxyalkylations I have withdrawn a substantial portion at theend of each step and continued oxyalkylation on a partial residualsample. This was not the case in this particular series. Certainexamples were duplicated as herein after noted and subjected tooxyalkylation with a different oxide.

Example 2c This example simply illustrates the further oxyalky1ation ofExample 10, preceding. As previously stated, theoxyalkylation-susceptible compound, to wit, Example 1b, present at thebeginning of the stage was obviously the same as at the end of the priorstage (Example 10), about 12.02 pounds. The amount of oxide present inthe initial step was 12.02 pounds, the amount of catalyst remained thesame, to wit, one pound, and the amount of solvent remained the same.The amount of oxide added was another 12.02 pounds, all addition ofoxide in these various stages being based on the addition of thisparticular amount. Thus, at the end of the oxyethylation step the amountof oxide added was a total of 24.04 pounds and the molal ratio ofethylene oxide to resin condensate was 54.7 to 1. The theoreticalmolecular weight was 3606.

The maximum temperature during the operation was C. to C. The maximumpressure was in the range of 15 to 20 pounds. The time period was alittle less than before, to wit, only 45 minutes.

Example 3c The oxyalkylation proceeded in the same manner described inExamples 10 and 20. There was no added solvent and no added catalyst.The oxide added was 12.02 pounds and the total oxide at the end of theoxyethylanon step was 36.06 pounds. The molal ratio of oxide tocondensate was 82.0 to 1. Conditions as far as temperature, pressure andtime were concerned were all the same is in Examples 10 and 2c. The timeperiod was one our.

Example 40 The oxyethylation was continued and the amount of oxide addedagain was 12.02 pounds. There was no added catalyst and no addedsolvent. The molal ratio of oxide to condensate was 109 to 1. Conditionsas far as temperature and pressure were concerned were the same as inprevious examples. The time period was slightly longer, to wit, 2 /2hours. The theoretical molecular weight at the end of the prior step was4808, and at the end of this step 6010. The reaction showed some slowmgup at this particular stage.

Example 5c The oxyethylation continued with the introduction of another12.02 pounds of ethylene oxide. No more solvent was introduced but .3pound caustic soda was added. The theoretical molecular weight at theend of the agitation period was 7212, and the molal ratio of oxide toresin condensate was 136.5 to 1. The time period, however, was slightlyless than before, to wit, 2 hours. Operating temperature and pressureremained the same as in the previous example.

Example 60 The same procedure was fallowed as in the previous examples.The amount of oxide added was another 12.02 pounds, bringing the totaloxide introduced to 72.12 pounds. The temperature and pressure duringthis period were the same as before. There was no added solvent. Thetime period was 3 hours.

9 Example 70 The same procedure was followed as in the previous sixexamples without the addition of more caustic or more solvent. The totalamount of oxide introduced at the e'nd of the period was 84.14-pounds.The theoretical molecular'weight'at the end of the oxyalkylation periodwa's96l6. The time required for the oxyethylation was the same as'in theprevious step, to wit, 3 hours.

Example 80 This wasthe final oxyethylation in this particular series.There was no added solvent and no added-catalyst. The totaltamountofoxide added at the end-of this step was 96.16 pounds. The theoreticalmolecular weight was 10,818; The molal ratio of oxide to resincondensate was 218.to one. Conditions as far as temperature and pressurewere concernednwere the same as in the previous examples. and the timerequired for oxyethylation was slightly longer than in the previousstep, to wit, 4 hours.

The same procedure as described in the previous examples was employed inconnection with a number of the other. condensates described previously.All these data have. been presented in tabular form in a series of fourtables, Tables III and IV, V and VI.

Injsubsequently every case a 25-gallon autoclave was employed, althoughin some instances the initial oxyethylation-.was. started in a l5-gallonautoclave and then transferred. to a 25-gallon autoclave. This isimmaterial'but. happened to be a matter of convenience only. The.solventiusedin all cases was xylene. The catalyst used was finelypowdered caustic soda.

Referring now to Tables ill and 1V, it will be noted that. compoundsthrough 400 were obtained by the use of ethylene oxide, whereas 41cthrough 80c were obtainedrby the..use. of. propylene oxide alone.

1 Thus, mreference to Table III it is to be noted as folows;

The example. number of each compound is indicated inthefirstcolumn.

The identity of. the oxyalkylation-susceptible compound, to wit, theresin condensate, is indicated in the second column.

The, amount. of. condensate is. shown. in the third column.

Assuming. that. ethylene oxide alone is employed, as happens .to.bethe.case in Examples 10 through 400, the amount of oxide present in theoxyalkylation derivative isshowu in column. 4, although in the initialstep since no oxideis present there is a blank.

When ethylene. oxide isused exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as acatalyst, and the 7th column shows the amount. of solvent employed.

The, 8th.c ol urnn can be ignored where a single oxide was, employed.

The9th column shows the theoretical molecular weight at.the ,end of theoxyalkylation period.

The v lQth column, states the amount of condensate present. in thereaction mass at the end of the period.

As pointed. out previously, in this. particular series the ramount of.reaction mass withdrawn for examination Was'so small that it was ignoredand for this reason the resin condensate in column 10 coincides with thefigure in column 3.

Column 11 shows the amount of ethylene oxide employed 1n the reactionmass at the end of the particular period Column 12 can be ignoredinsofar that no propylene oxide was employed.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide wasemployed.

Referring now to Table VI. It is to be noted that the first columnrefers to Examples lc, 20, 30, etc.

Thefsecond column gives the maximum temperature employed during theoxyalkylation step and the third column; gives the maximum pressure.

The. fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amountof the compound, including the solvent present, with several volumes ofwater, xylene and kerosene. It sometimes happens. that although xylenein comparatively small amounts will dissolve. in the concentratedmaterial, whenv the concentrated material in turn is diluted with xyleneseparation takes place.

Referring to Table IV, Examples 410 through 80c are the counterparts ofExamples 1c through 400, except that the oxide employed ispropylenefoxide instead of ethylene oxide. Therefore, as explainedpreviously, four columns are blank, to wit, columns 4, 8, l1 and 15.

Reference is now made to Table V. It is to be noted these compounds aredesignated by d numbers, 1d, 2d, 3d, etc., through and including 32d.They are derived, in turn, from compounds in the .c series, for example,37c, 40c, 46c, and. 77c. These compounds involve the use of bothethylene oxide and propylene oxide. Since compounds 1c through 400 wereobtained by the use of ethylene oxide, it is obvious that those obtainedfrom 370 and 40c, involve the use of ethylene oxide first, and propyleneoxideafterward. inversely, those compounds obtained from 460 and 770obviously come from a prior series in which propylene oxide was usedfirst.

In the preparation of. this series indicated by the small letter d, as1d, 2d, 3d, etc., the initial 0 series such as 370, 40c, 46c, and 770,were duplicated and the oxyalkylation stopped at the point designatedinstead of being carried further as may have been the case in theoriginal oxyalkylation. step. Then oxyalkylation proceeded by usingv thesecond oxide as indicated by the previous explanation, to wit, propyleneoxide in ld through 16d, and ethylene oxide in 17a through 320',inclusive.

In examining. the table beginning with 1d, it will be noted that theinitial product, i. e., 37c, consisting of the reaction product.involving 12.02 pounds of. the resin condensate, 30.05. pounds ofethylene. oxide, 1.0 pound of caustic soda, and.5.0 pounds of thesolvent.

It is to be noted that reference to the catalyst in Table V refers tothe total amount of catalyst, i. e., the catalyst present from the firstoxyalkylation step plus added catalyst, if any. The same is true inregard to the solvent. Reference to the solvent refers tothe totalsolvent present, i. e., that from the first oxyalkylation step plusadded solvent, if any.

In this series, it will be noted that the theoretical molecular weightsare given prior to the oxyalkylation step and after the oxyalkylationstep, although the value at the end of one step is the value at thebeginning of the next step, except obviously at the very start the valuedepends on thetheoretical molecular Weight at the end of the initialoxyalkylation step; i. e., oxye thylation for ld through 16d, andoxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of bothoxides to the resin condensate are, included.

The data given in regard to the operating conditions is substantiallythe same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts,or have small amounts, of the solvents as indicated by. the figures inthe tables. If desired the solvent may be removed by distillation, andparticularly vacuum distillation. Such distillation also may removetraces or small amounts of uncombined oxide, if present and volatileunder the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide incombination one need not first use one oxide and then the other, but onecan mix the two oxides and thus obtain what may be termed an indifferentoxyalkylation, i. e., no attempt to selectively add one and then theother, or any other variant.

Needless to say, one could start with ethylene oxide and then usepropylene oxide, and then go back to ethylene oxide; or, inversely,start with propylene oxide, then use ethylene oxide, and then go back topropylene oxide; or, one could use a combinationin which butylene oxideis used along with either one of the two oxides just mentioned, or acombination of both of them.

reason is amber with a reddish The colors of the products usually varyfrom a reddish amber tint to a definitely red, and amber. The

primarily that no effort is made to obtain colorless resins initiallyand the resins themselves may be yellow, amber, or even dark amber.Condensation of a nitrogenous product invariably yields a darker productthan the original resin and usually has a reddish color. adds nothing tothe color but one may use petroleum solvent. oxyalkylation generallytends to yield lighter colored products and the more oxide employed thelighter the color of the product. Products can be prepared in which thefinal color is a lighter tint. Such products can be decolorized by theuse of clays, bleaching chars, etc. As far as use in demulsification isconcerned, or some other industrial uses, there is no justification forthe cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present iscomparatively small and it need not be removed. Since the products perse are alkaline due to the presence of a basic nitrogen, the removal ofthe alkaline catalyst is somewhat more diificult than ordinarily is thecase for the reason that if one adds hydrochloric acid, for example, toneutralize the alkalinity one may partially neutralize the basicnitrogen radical also. The preferred procedure is to ignore the presenceof the alkali unless it is objectionable or else add a The solventemployed, if xylene,

a darker colored aromatic stolchiometric amount of concentratedhydrochloric acid equal to the caustic soda present.

PART 5 In practicing the present process, the treating or demulsifyingagent is used in the conventional way, well known to the art, described,for example, in Patent 2,626,929, dated January 27, 1953, Part 3, andreference is made thereto for a description of conventional proceduresof demulsifying, including batch, continuous, and down-the-holedemulsification, the process essentially involving introducing a smallamount of demulsifier into a large amount of emulsion with adequateadmixture with or without the application of heat, and allowing the miX-ture to stratify.

In many instances the oxyalkylated products herein specified asdemulsifiers can be conveniently used without dilution. However, aspreviously noted, they may be diluted as desired with any suitablesolvent. For instance, by mixing 75 parts by weight of an oxyalkylatedderivative, for example, the product of Example 40 with 15 parts byweight of xylene and 10 parts by weight of isopropyl alcohol, anexcellent demulsifier is obtained. Selection of the solvent will vary,depending upon the solubility characteristics of the oxyalkylatedproduct, and of course will be dictated in part by economicconsiderations, i. e., cost.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsifier. A mixture which illustrates such combination is thefollowing:

oxyalkylated derivative, for example, the product of Example 40, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic Isopropyl alcohol, 5%.

The above proportions are all weight percents.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyalkylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in th ll fi fi polypropylated naphthalene petroleumsolvent, 15%;

absence of trifunctional phenols; said phenol being of the formula OH inwhich R is an aliphatic hydrocarbon radical having at least 4 and notmore than 24 carbon atoms and substituted in the 2,4,6 position; (b) abasic hydroxylated polyamine having at least one secondary amino groupand having not over 32 carbon atoms in any radical attached to any aminonitrogen atom, and with the further proviso that the polyamine be freefrom any primary amino radical, any substituted imidazoline radical, andany substituted tetrahydropyrimidine radical; and (0) formaldehyde; saidcondensation reaction being conducted at a temperature sufficiently highto eliminate water and below the pyrolytic point of the reactants andresultants of reaction; and with the proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptible; followed by an oxyalkylation step by means ofan alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide.

2. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyalkylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 24 carbon atomsand substituted in the 2,4,6 position; (b) a basic hydroxylatedpolyamine having at least one secondary amino group and having not over32 carbon atoms in any radical attached to any amino nitrogen atom, andwith the further proviso that the polyamine be free from anyprimaryamino radical, any substituted imidazoline radical, and any substitutedtetrahydropyrimidine radical; and (0) formaldehyde; said condensationreaction being conducted at a temperature sufiiciently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in whicheach ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom of reaction with a resin molecule; with the added provisothat the ratio of reactants be approximately 1, 2 and 2,- respectively;with the further proviso that said procedure involve the use of asolvent; and with the final proviso that the resinous condensationproduct resulting from the process be heat-stable andoxyalkylation-susceptible: fol; lowed by an oxyalkylation step by meansof an alphabeta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methyl.- glycide.

3. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of first condensing (a)an oxyalkyla-- tion-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having anaverage molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to in which R is an aliphatic hydrocarbon radical having atleast 4 and not more than 14 carbon atoms and substituted in the 2,4,6position; (b) a basic hydroxylated polyamine having at least onesecondary amino group and having not over 32 carbon atoms in any radicalattached to any amino nitrogen atom, and with the further proviso thatthe polyamine be free from any primary amino radical, any substitutedimidazoline radical, and any substituted tetrahydropyrimidine radical;and formaldehyde; said condensation reaction being conducted at atemperature sufficiently high to eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction, with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomof reaction with a resin molecule; with the added proviso that the ratioof reactants be approximately 1, 2 and 2 respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide.

4. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a dernulsifierincluding the products obtained in the process of first condensing (a)an oxyalkylation-susceptible, fusible, non-"oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to rnethylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is an aliphatichydrocarbon radical having at least 4 and not more than 14 carbon atomsand substituted in the 2,4,6 position; (b) a basic hydroxylatedpolyamine having at least one secondary amino group and having not over32 carbon atoms in any radical attached to any amino nitrogen atom, andwith the further proviso that the polyamine be free from any primaryamino radical, any substituted imidazoline radical, and any substitutedtetrahydropyrimidine radical; and (0) formaldehyde; said condensationreaction being conducted at a temperature above the boiling point ofwater and below 150 C., with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehydederived methylene bridge connectingthe amino nitrogen atom of reaction with a resin molecule; with theadded proviso that the ratio of reactants be approximately 1, 2 and 2,respectively; with the further proviso that said procedure involve theuse of a solvent; and with the final proviso that the resinouscondensation product resulting from the process be heat-stable andoxyalkylation-susceptlble; followed by an oxyalkylation step by means ofan alpha-beta alkylene oxide having not more than 4- carbon atoms andselected from the class consisting of ethylene oxide, propylene oxidebutylene oxide, glycide and methylglycide.

5. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion of the action of a clemulsifierincluding the products obtained in the process of first condensing (a)an oxyalkylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to a tleast 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is apara-substituted aliphatic hydrocarbon radical having at least 4 and notmore than 14 carbon atoms and substituted in the 2,4,6 position; (b) abasic hydroxylated polyamine having at least one secondary amino groupand having not over 32 carbon atoms in any radical attached to any aminonitrogen atom, and with the further proviso that the polyamine be freefrom any primary amino radical, any substituted imidazoline radical, andany substituted tetrahydropyrimidine radical; and (0) formaldehyde; saidcondensation reaction being conducted at a temperature above the boilingpoint of water and below C., with the proviso that the condensationreaction be conducted so as to produce a significant portion of theresultant in which each of the three reactants have contributed part ofthe ultimate molecule by virtue of a formaldehyde-derived methylenebridge connecting the amino nitrogen atom of reaction with a resinmolecule; with the added proviso that the ratio of reactants beapproximately 1, 2 and 2, respectively; with the further proviso thatsaid procedure involve the use of a solvent; and with the final provisothat the resinous condensation product resulting from the process beheatstable and oxyalkylation-susceptible; followed by an oxyalkylationstep by means of an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide and methylglycide.

6. The process of claim 1 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene, are sufl'icient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

7. The process of breaking petroleum emulsions as delined in claim 1wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

8. The process of claim 7 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free and (c) the salt of hydroxy aceticacid, in an equal weight of xylene, are sufficient to produce anemulsion when said xylene solution is shaken vigorously with l to 3volumes of water.

9. The process of claim 2 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hvdroxyacetic acid, in an equal Weight of xylene, are sufficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

10. The process of breaking petroleum emulsions as defined in claim 2wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

11. The process of claim 10 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactemplcyed in the form of a member of the class consisting of (a) theanhydro base as is,

(b) the free base, and (c) the salt of hydroxy acetic acid, in an equalweight of xylene, are sufiicient to produce an emulsion when said xylenesolution is shaken vigorously with l to 3 volumes of water,

12. The process of claim 3 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene, are sufficient to produce anemulsion when said xylene solution is shaken Vigorously with 1 to 3volumes of water.

13. The process of breaking petroleum emulsions as defined in claim 3wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

14. The process of claim 13 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene, are sufiicient to produce anemulsion when said xylene solution is shaken vigorously with l to 3volumes of water.

15. The process of claim 4 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene, are sufficient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

16. The process of breaking petroleum emulsions as defined in claim 4wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

17. The process of claim 16 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, b) the free base, and (c) the salt of hydroxy aceticacid, 111 an equal Weight of xylene, are suflicient to produce anemulsion when said xylene solution is shaken vigorously with l to 3volumes of water.

18. The process of claim 5 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxy acid,in an equal weight of xylene, are sufficient to produce an emulslon whensaid xylene solution is shaken vigorously with 1 to 3 volumes of water.

19. The process of breaking petroleum emulsions as defined in claim 5wherein the oxyalkylation step of the manufacturing process is limitedto the use of both ethylene oxide and propylene oxide in combination.

20. The process of claim 19 with the proviso that the hydrophileproperties of the product of the oxyalkylated condensation reactionemployed in the form of a member of the class consisting of (a) theanhydro base as is, (b) the free base, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene, are suflicient to produce anemulsion when said xylene solution is shaken vigorously with 1 to 3volumes of water.

References Eited in the file of this patent UNITED STATES PATENTS NumberName Date 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote et a1. Mar.7, 1950 2,499,368 De Groote et al. Mar. 7, 1950 2,542,011 De Groote eta1. Feb. 20, 1951

1. A PROCESS FOR BREAKING PETROLEUM EMULSION OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF FIRST CONDENSING (A)AN OXYALKYLATION-SUSCEPTIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE,WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGEMOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLICNUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARDTO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTIONBETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMEDIN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEINGOF THE FORMULA